US5558758A - Electrodeposited composite coatings - Google Patents

Electrodeposited composite coatings Download PDF

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Publication number
US5558758A
US5558758A US08/211,506 US21150694A US5558758A US 5558758 A US5558758 A US 5558758A US 21150694 A US21150694 A US 21150694A US 5558758 A US5558758 A US 5558758A
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United States
Prior art keywords
particles
matrix
coating according
cobalt
coating
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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US08/211,506
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English (en)
Inventor
John Foster
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Praxair ST Technology Inc
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Praxair ST Technology Inc
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Assigned to PRAXAIR S.T. TECHNOLOGY, INC. reassignment PRAXAIR S.T. TECHNOLOGY, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BAJ COATINGS LIMITED
Assigned to BAJ COATINGS LIMITED reassignment BAJ COATINGS LIMITED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: FOSTER, JOHN
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C25D15/02—Combined electrolytic and electrophoretic processes with charged materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/922—Static electricity metal bleed-off metallic stock
    • Y10S428/9335—Product by special process
    • Y10S428/934—Electrical process
    • Y10S428/935—Electroplating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12486—Laterally noncoextensive components [e.g., embedded, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12937—Co- or Ni-base component next to Fe-base component

Definitions

  • This invention relates to electrodeposited composite coatings, i.e. coatings which consist of an electrolytically or electrolessly plated metal matrix with included particles which are codeposited with the matrix.
  • the particles are suspended in the electrolyte containing the metal ions for the matrix and are substantially insoluble in the electrolyte and, during the plating operation, become included in the plated matrix.
  • the coatings may be applied to a variety of components subjected to wear such as aero-engine components, particularly those likely to operate at elevated temperatures, bearing surfaces, rocket nozzles, and tubes and nozzles carrying abrasive substances.
  • the coatings may be applied to the whole component but more frequently they will be applied to only a portion of its surface.
  • the electrodeposition technique is particularly suitable to the protection of selected areas and the coating of complex, re-entrant and inaccessible areas do not present any great problems.
  • the coatings are particularly suited to use on gas turbine blades.
  • Our United Kingdom patent GB-A-1358538 describes a composite coating comprising, as deposited, a matrix which is at least 50% by weight cobalt and particles included in the matrix which are at least 50% by weight chromium carbide, at least 50% by weight of the particles having a particle size of less than ten microns and preferably between 2 and 5 microns.
  • GB-A-1358538 indicates that although preferably all the particles have a size between 2 and 5 microns it may not be practicable completely to avoid a small quantity of fines below 2 microns and possibly some larger particles due, for example, to agglomeration but states that preferably more than 80% by weight of the particles lie within the specified limits, i.e. between 2 and 5 microns.
  • the processes described in GB-A-1358538 have been used for approximately twenty years with very great success.
  • the particles which have been used have had a size distribution within the range set out, i.e. most of the particles having a size between 2 and 5 ⁇ m.
  • the particles used have been much as received from the supplier but, as will be explained below, some small adjustment has sometimes been made by removing a proportion of the larger particles.
  • coatings are produced having an as-deposited composition range of between 13 and 20 percent by weight of chromium carbide dispersed in a cobalt matrix.
  • the as-deposited coatings are somewhat modified by diffusion produced by heat treatment and/or heat resulting from use of the components carrying the coatings.
  • size is meant that half the particles by weight have a size less than 7 ⁇ m and half have a size equal to or larger than 7 ⁇ m.
  • the invention may be said to reside in using particles at least 80% by weight of which exceed 4 ⁇ m in size and at least 80% of which lie within a range of 4 ⁇ m to 8 ⁇ m (and preferably with the upper end of the range not exceeding 20 ⁇ m).
  • the particles are substantially evenly distributed in size across the range.
  • the invention also includes, according to a further aspect, a method of producing a coating comprising depositing by electrodeposition or by electroless deposition a matrix of cobalt and codepositing with the matrix particles of chromium carbide suspended in the plating bath, 80% by weight of the particles falling within the size range of 4 to 12 ⁇ m.
  • the invention is particularly suited to coatings in which substantially all the particles are chromium carbide and the matrix is substantially all cobalt.
  • the deposited coatings will usually be heat treated, for example at a temperature above 500° C. for a period in excess of two hours, to produce diffusion of material between the matrix and the particles.
  • FIG. 1 is a perspective view of the apparatus
  • FIG. 2 is a side elevation of the apparatus
  • FIG. 3 is a front elevation of the apparatus
  • FIG. 4 is a graph showing particle size distributions.
  • the apparatus shown in the drawings comprises a vessel or container 1 having a parallelepiped shaped upper portion 2 and a downwardly tapering lower portion 3 in the form of an inverted pyramid which is skewed so that one side face 4 forms a continuation of one side face 5 of the upper portion.
  • the vessel 1 contains a partition 6 which lies in a vertical plane parallel to the side faces 4 and 5 of the vessel and makes contact at its side edges 7 and 9 with the adjacent vertical and sloping faces of the vessel.
  • the partition thus divides the vessel into a larger working zone 9 and a smaller return zone 11.
  • the partition 6 terminates at a horizontal edge 12 above the bottom of the vessel to afford an interconnection 13 between the working zone 9 and the return zone 11.
  • the partition 6 terminates at a horizontal edge 14 below the top edges of the vessel 1.
  • an air inlet 15 which is connected to an air pump (not shown).
  • a jig 16 mounted in the working zone 9 , the jig 16 being mounted for rotation about a horizontal axis parallel to the plane of the partition and motor means (not shown) is provided to rotate the jig.
  • Conductors are provided to apply a voltage to the workpiece mounted on the jig 16 relative to a cobalt anode which is suspended in the working zone.
  • the workpiece is mounted on the jig 16 which is positioned in the vessel as shown.
  • the vessel is filled to a level 17 above the top edge 14 of the partition 6 with a cobalt plating solution containing particles of chromium carbide to be co-deposited.
  • Air is admitted to the inlet 15 and this rises up the return zone 11, raising solution and entrained particles.
  • the air escapes and the solution and particles flow over the broad crested weir formed by the top edge 14 of the partition and flow down past the workpiece on the rotating jig 16.
  • the particles tend to settle and slide down the inclined sides of the vessel towards the interconnetion 13 where they are again entrained in the solution and carried round again.
  • the article to be coated is prepared as follows. The article is first degreased by immersion in trichloroethylene or by swabbing with lint free material soaked in acetone. Areas not to be electroplated are then masked. The areas to be plated are then cleaned either mechanically by blasting with alumina shot or chemically with a suitable cleaning medium such as an acid pickle.
  • the current is then switched on and the prepared article placed in the solution.
  • the air flow is adjusted to a suitable rate and the current is adjusted to give the correct current density which may, for example, be between 10 and 150 amps per square foot of surface being plated at a voltage of 15 volts.
  • the article is withdrawn and is washed and dried.
  • a test piece of steel was coated in the apparatus shown in FIGS. 1 to 3.
  • the tank contained an electrolytic bath of the following composition:
  • the bath also contained 500 g/l of chromium carbide (Cr 3 C 2 ) powder having a particle size distribution according to Curve R in the accompanying graph (FIG. 4) the y-axis of which represents the percentage by weight of the particles having a size below a size indicated in ⁇ ms on the x-axis.
  • Curve R shows a size distribution in accordance with the present invention.
  • the bath had a pH of 4.7 and during deposition it was maintained at a temperature of approximately 50° C.
  • test piece was first degreased in trichlorethylene vapour and was then shot blasted with grade 50 ⁇ alumina shot.
  • the pump 3 was then switched on and when the particles had become distributed through the bath the test piece was connected to the current supply as the cathode and was inserted in the bath.
  • the current was adjusted to give a density of 4 A/dm 2 . After a time sufficient to produce a coating thickness of 125 ⁇ m the test piece was removed from the bath and was washed and dried.
  • test piece was then heat treated by being maintained at a temperature of 1,000° C. for four hours followed by an oil quench.
  • Curve P shows the size distribution of the as-received powder
  • Curve Q shows the size distribution of the as-received powder modified by the removal of a proportion of the larger particles as has been the practice hitherto.
  • the coatings were subjected to a high PV environment, namely a Hertzian contact stress of 200 N/mm 2 , a sliding velocity of 0.13 m/s and a temperature of 450° C. It was found that Coating A had a hardness (Vickers Hardness Number VHN) of 350 while Coating B had a hardness of 500 and that Coating A had a Rubbing Wear Factor indicating the amount of wear of 4 while Coating B had a Rubbing Wear Factor of 0.06. It will be appreciated that the tests show that Coating B was much superior to Coating A.
  • coatings in accordance with the present invention can be produced by the methods described in GB-A-1358538 and the apparatus described in GB-A-1218179, GB-A-1329081 and GB-A-2182055 to which reference should be made for further details.
  • Tests were also conducted to compare Coating B with well-known wear-resistant coatings and the results are shown in Table 2.
  • the tests were conducted by reciprocating a loaded round-bottomed disc of 15 mm diameter on a flat plate.
  • the underside of the disc had a part-spherical shape with a diameter of 30 mm.
  • the load on the disc was 2N
  • the disc was reciprocated at a speed of 0.13 m/sec
  • the test was conducted at a temperature of 450° C. and had a duration of 180 minutes. Both the underside of the disc and the upper surface of the plate were coated with the same material.
  • the underside of the disc was measured for wear and the wear is given in the table in m 3 /Nmx10 -15 . For each material, two samples were prepared and tested. It will be seen from the table that Coating B suffered very significantly lower wear than any of the other materials.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Chemically Coating (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Paints Or Removers (AREA)
  • Conductive Materials (AREA)
  • Physical Vapour Deposition (AREA)
US08/211,506 1992-07-06 1993-08-05 Electrodeposited composite coatings Expired - Lifetime US5558758A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB9216706 1992-08-06
GB929216706A GB9216706D0 (en) 1992-08-06 1992-08-06 Electrodeposited composite coatings
PCT/GB1993/001659 WO1994003656A1 (en) 1992-08-06 1993-08-05 Electrodeposited composite coatings

Publications (1)

Publication Number Publication Date
US5558758A true US5558758A (en) 1996-09-24

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US08/211,506 Expired - Lifetime US5558758A (en) 1992-07-06 1993-08-05 Electrodeposited composite coatings

Country Status (11)

Country Link
US (1) US5558758A (ru)
EP (1) EP0612360B1 (ru)
JP (1) JP2767496B2 (ru)
AU (1) AU661610B2 (ru)
CA (1) CA2120615C (ru)
DE (1) DE69422435T2 (ru)
ES (1) ES2140529T3 (ru)
GB (1) GB9216706D0 (ru)
RU (1) RU2127333C1 (ru)
SG (1) SG49744A1 (ru)
WO (1) WO1994003656A1 (ru)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5935407A (en) * 1997-11-06 1999-08-10 Chromalloy Gas Turbine Corporation Method for producing abrasive tips for gas turbine blades
US20040048003A1 (en) * 2002-01-15 2004-03-11 Andre Jeutter Method for coating a substrate having holes
US20040079648A1 (en) * 2002-10-15 2004-04-29 Alstom (Switzerland) Ltd. Method of depositing an oxidation and fatigue resistant MCrAIY-coating
EP1426458A1 (en) * 2002-12-06 2004-06-09 ALSTOM Technology Ltd Method of locally depositing a MCrAlY coating
EP1443125A1 (en) * 2003-01-17 2004-08-04 ANSALDO RICERCHE S.r.l. - Società per lo Sviluppo di Nuove Tecnologie CoCrC coating for surfaces liable to consumption
US20040159552A1 (en) * 2002-12-06 2004-08-19 Alstom Technology Ltd. Method of depositing a local MCrAIY-coating
EP1460152A1 (en) * 2003-03-21 2004-09-22 ALSTOM Technology Ltd A method of depositing a wear resistant seal coating and seal system
US20070170068A1 (en) * 2006-01-24 2007-07-26 Usc, Llc Electrocomposite coatings for hard chrome replacement
US20070172695A1 (en) * 2006-01-26 2007-07-26 Hamilton Sundstrand Corporation Low cost, environmentally favorable, chromium plate replacement coating for improved wear performance
US20100096811A1 (en) * 2004-06-23 2010-04-22 Advanced Components & Materials, Inc. Electro-composite coating for flexible seals and method of applying the same
US20100148752A1 (en) * 2004-08-31 2010-06-17 Steven Douglas Jons Method for testing separation modules
US9957629B2 (en) 2014-08-27 2018-05-01 Praxair S.T. Technology, Inc. Electroplated coatings

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009074141A (ja) * 2007-09-21 2009-04-09 Komatsu Ltd 合金メッキ層の形成方法及び構造部品
JP2009242862A (ja) * 2008-03-31 2009-10-22 Komatsu Ltd 合金メッキ層の形成方法及びコーティング部材
DE102010024224B4 (de) * 2010-06-18 2016-08-18 MTU Aero Engines AG Verfahren und Vorrichtung zum Aufbringen einer Dispersionsschicht mit einem Matrixwerkstoff und Feststoffteilchen

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3532608A (en) * 1967-09-29 1970-10-06 United States Steel Corp Method of treating steel and electrolyte therefor
GB1358538A (en) * 1971-06-08 1974-07-03 Bristol Aerojet Ltd Electrodeposited composite coatings
JPS523894A (en) * 1975-06-26 1977-01-12 Ajinomoto Co Inc Isolation of urokinase
JPS61133399A (ja) * 1984-12-03 1986-06-20 Nippon Steel Corp 鋼板の燐酸塩処理方法
US4789441A (en) * 1984-10-05 1988-12-06 John Foster Metallic protective coatings and method of making

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2014189B (en) * 1977-12-21 1982-06-09 Bristol Aerojet Ltd Processes for the electrodeposition of composite coatings

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3532608A (en) * 1967-09-29 1970-10-06 United States Steel Corp Method of treating steel and electrolyte therefor
GB1358538A (en) * 1971-06-08 1974-07-03 Bristol Aerojet Ltd Electrodeposited composite coatings
JPS523894A (en) * 1975-06-26 1977-01-12 Ajinomoto Co Inc Isolation of urokinase
US4789441A (en) * 1984-10-05 1988-12-06 John Foster Metallic protective coatings and method of making
JPS61133399A (ja) * 1984-12-03 1986-06-20 Nippon Steel Corp 鋼板の燐酸塩処理方法

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5935407A (en) * 1997-11-06 1999-08-10 Chromalloy Gas Turbine Corporation Method for producing abrasive tips for gas turbine blades
US6194086B1 (en) 1997-11-06 2001-02-27 Chromalloy Gas Turbine Corporation Method for producing abrasive tips for gas turbine blades
US20040048003A1 (en) * 2002-01-15 2004-03-11 Andre Jeutter Method for coating a substrate having holes
US20040079648A1 (en) * 2002-10-15 2004-04-29 Alstom (Switzerland) Ltd. Method of depositing an oxidation and fatigue resistant MCrAIY-coating
EP1426458A1 (en) * 2002-12-06 2004-06-09 ALSTOM Technology Ltd Method of locally depositing a MCrAlY coating
US20040159552A1 (en) * 2002-12-06 2004-08-19 Alstom Technology Ltd. Method of depositing a local MCrAIY-coating
US20040163583A1 (en) * 2002-12-06 2004-08-26 Alstom Technology Ltd. Method of depositing a local MCrAIY-coating
EP1443125A1 (en) * 2003-01-17 2004-08-04 ANSALDO RICERCHE S.r.l. - Società per lo Sviluppo di Nuove Tecnologie CoCrC coating for surfaces liable to consumption
US7445854B2 (en) 2003-03-21 2008-11-04 Alstom Technology Ltd Seal system
US20040185294A1 (en) * 2003-03-21 2004-09-23 Alstom Technology Ltd Method of depositing a wear resistant seal coating and seal system
US7851027B2 (en) 2003-03-21 2010-12-14 Alstom Technology Ltd Method of depositing a wear resistant seal coating and seal system
EP1460152A1 (en) * 2003-03-21 2004-09-22 ALSTOM Technology Ltd A method of depositing a wear resistant seal coating and seal system
US20100047460A1 (en) * 2003-03-21 2010-02-25 Alstom Technology Ltd. Method of depositing a wear resistant seal coating and seal system
US7815784B2 (en) * 2004-06-23 2010-10-19 Advanced Components & Materials, Inc. Electro-composite coating for flexible seals and method of applying the same
US20100096811A1 (en) * 2004-06-23 2010-04-22 Advanced Components & Materials, Inc. Electro-composite coating for flexible seals and method of applying the same
US20100148752A1 (en) * 2004-08-31 2010-06-17 Steven Douglas Jons Method for testing separation modules
US20070170068A1 (en) * 2006-01-24 2007-07-26 Usc, Llc Electrocomposite coatings for hard chrome replacement
US20110086239A1 (en) * 2006-01-24 2011-04-14 Usc, Llc Electrocomposite coatings for hard chrome replacement
US8445114B2 (en) * 2006-01-24 2013-05-21 Hamilton Sundstrand Corporation Electrocomposite coatings for hard chrome replacement
US20070172695A1 (en) * 2006-01-26 2007-07-26 Hamilton Sundstrand Corporation Low cost, environmentally favorable, chromium plate replacement coating for improved wear performance
US7897265B2 (en) 2006-01-26 2011-03-01 Hamilton Sundstrand Corporation Low cost, environmentally favorable, chromium plate replacement coating for improved wear performance
US20110114495A1 (en) * 2006-01-26 2011-05-19 Hamilton Sundstrand Corporation Low cost, environmentally favorable, chromium plate replacement coating for improved wear performance
US8246807B2 (en) 2006-01-26 2012-08-21 Hamilton Sundstrand Corporation Low cost, environmentally favorable, chromium plate replacement coating for improved wear performance
US9957629B2 (en) 2014-08-27 2018-05-01 Praxair S.T. Technology, Inc. Electroplated coatings

Also Published As

Publication number Publication date
ES2140529T3 (es) 2000-03-01
GB9216706D0 (en) 1992-09-23
SG49744A1 (en) 1998-06-15
CA2120615C (en) 2000-10-17
RU2127333C1 (ru) 1999-03-10
DE69422435D1 (de) 2000-02-10
JPH06511519A (ja) 1994-12-22
EP0612360B1 (en) 2000-01-05
DE69422435T2 (de) 2000-08-03
WO1994003656A1 (en) 1994-02-17
AU661610B2 (en) 1995-07-27
CA2120615A1 (en) 1994-02-17
AU4721693A (en) 1994-03-03
EP0612360A1 (en) 1994-08-31
JP2767496B2 (ja) 1998-06-18

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